Present methods for partially oxidizing organic compounds include reactions of mixtures of oxygen with the organic compounds at elevated temperatures with or without reaction-promoting additives such as hydrogen bromide or solid catalysts, e.g. tellurium oxide. Fluorine has been disclosed as an ignition aid for mixtures of hydrocarbon and oxygen. V. A. Poluektov et al., Zhur. Fiz. Khim. (Russian Journal of Physical Chemistry), vol. 43, p. 1747, (English translation: Russian Journal of Physical Chemistry, vol. 43 (7) 1969 Pages 977-980 have reported the results of experiments in which measured amounts of fluorine were injected into mixtures of oxygen and hydrocarbon, specifically methane, butane, cyclohexane, and butene in a closed reaction vessel at controlled mixture ratios, temperatures, and pressures. The ratio of oxygen to hydrocarbon was maintained at CO.sub.2 + H.sub.2 O stoichiometry and the percentage of injected fluorine was varied. Ignition resulting in explosion or flame occurred when the pressure of the mixture exceeded a critical limit which was found to depend on the nature of the hydrocarbon, the percentage of fluorine, and the temperature. The authors found that the addition of the fluorine markedly reduced the ignition pressure and temperature with increasing concentrations of fluorine to regimes very substantially below atmospheric pressure at ambient temperatures. For example, in the case of butane, injection of 4% and 7% of fluorine based on the F.sub.2 -O.sub.2 mixture resulted in ignition when the pressure in the reaction vessel exceeded the following critical limits at the following temperatures: 4% F.sub.2 Temp. .degree.C 0 24 100 Critical limit, mm Hg 150 92 208 7% F.sub.2 Temp. .degree.C 0 24 100 Critical limit, mm Hg 100 45 55
Poluektov et al. disclose that aldehydes were found in the low-pressure ignition "peninsula" below the critical ignition limits in the aforedescribed 4% fluorine, butane, and oxygen mixture, namely in a regime wherein the ignition pressure varies from 92 mm to 208 mm Hg (the maximum ignition pressure in the peninsula) over a temperature range of 24.degree.C to 100.degree.C, and is further markedly reduced by small increases in the amount of fluorine. Practical production of oxygenated organic compounds within the extremely limited, very low-pressure conditions required by the Poluektov et al process would be hazardous and very costly.
The reported results of Poluektov et al establish the generally accepted "hypergolic" effect of reactive fluorine in the ignition of hydrocarbon-oxygen mixtures and do not suggest that fluorine could be effectively used as an activating agent in controlled flameless partial oxidation of organic compounds, or that such controlled oxidation could be carried out continuously at ambient pressures and temperatures with the same reactive components in ratios which the prior art has found to be instantaneously ignitive or explosive even at greatly reduced pressures. It is apparent that different reaction mechanisms occur in the continuous flow process of the invention as compared with those occurring in the prior art processes exemplified by Poluektov et al., but these different mechanisms are not as yet clearly understood.
The process of the invention has important advantages over other prior art processes for the production of oxygenated organic compounds since it can be carried out continuously at ambient temperature and pressure with a gaseous activating agent which forms a continuously removable gaseous product effluent, e.g. hydrogen fluoride. In addition to eliminating the costly requirement for maintaining high temperature (and in some cases, high pressure) conditions for reaction, the present process broadens versatility of the reaction and reaction products by broadening the range of reactive conditions. It is well known, for example, that the reaction mechanisms of organic compounds vary not only in degree but in kind with increasing temperature.